The process for ethynylating alpha,beta-unsaturated ketones for producing tertiary acetylenic alcohols is old and well known. See U.S. Pat. No. 3,709,946, Jan. 9, 1973, U.S. Pat. No. 3,082,260, Mar. 19, 1963, and U.S. Pat. No. 3,283,014, Nov. 1, 1966. A review concerning the hitherto used ethynylation reactions is given to T. F. Rutledge, Acetylenic Compounds, Reinhold Book Corporation (1968), p. 46-84 and 166-196. According to the classical process, ethynylation is carried out with sodium acetylide in liquid ammonia, as well as with calcium or lithium acetylide U.S. Pat. No. 2,425,201; W. Oroshnik et al., J. Amer. Chem. Soc. 71 (1949) 2062-2065. However, in these cases, alpha,beta-unsaturates ketones are generally obtained only small yields, since these ketones partially polymerize in ammonia. On the other hand, the monolithium acetylide spontaneously decomposes upon isolation from ammonia to dilithium acetylide (lithium carbide) and acetylene [R. J. Tedeschi et al., J. Org. Chem. 34 (1969) 435-438]. The high yields published for a process with the monolithium acetylide-ethylene-diamine complex in an organic solvent [O. F. Beumel et al., J. Org. Chem. 28 (1963) 2775-2779] could not be reproduced [K. R. Martin et al., J. Org. Chem. 33 (1968) 778-780], since the ethylenediamine liberated in the reaction caused self-condensation and polymerization of the alpha,beta-unsaturated ketones.
A newer ethynylation process, in which alkali metal acetylides are stabilized in ethers with non-basic compounds (U.S. Pat. No. 3,576,889), provides to some extent very good yields. However, this procedure is poorly suited to large-scale technical syntheses, since foreign substances in large-scale processes frequency cause trouble. Furthermore, these foreign substances must subsequently be further separated. Moreover, expensive lithium amide must be employed in the preferred embodiment of this process.